JPH03173849A - Production of cis-8-dodecenylacetate - Google Patents
Production of cis-8-dodecenylacetateInfo
- Publication number
- JPH03173849A JPH03173849A JP25460690A JP25460690A JPH03173849A JP H03173849 A JPH03173849 A JP H03173849A JP 25460690 A JP25460690 A JP 25460690A JP 25460690 A JP25460690 A JP 25460690A JP H03173849 A JPH03173849 A JP H03173849A
- Authority
- JP
- Japan
- Prior art keywords
- cis
- chloride
- reaction
- dodecenyl
- bromo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- SUCYDSJQVVGOIW-WAYWQWQTSA-N 8Z-Dodecenyl acetate Chemical compound CCC\C=C/CCCCCCCOC(C)=O SUCYDSJQVVGOIW-WAYWQWQTSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 12
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- PHHNNDKXQVKJEP-UHFFFAOYSA-N 1-bromo-5-chloropentane Chemical compound ClCCCCCBr PHHNNDKXQVKJEP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000877 Sex Attractant Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000000397 acetylating effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract description 2
- 241000659001 Grapholitha molesta Species 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- -1 olefin compounds Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- DCBJCKDOZLTTDW-UHFFFAOYSA-N 5-chloropentan-1-ol Chemical compound OCCCCCCl DCBJCKDOZLTTDW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- SJSWRKNSCWKNIR-UHFFFAOYSA-N azane;dihydrochloride Chemical compound N.Cl.Cl SJSWRKNSCWKNIR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 2
- SUCYDSJQVVGOIW-UHFFFAOYSA-N dodec-8-enyl acetate Chemical compound CCCC=CCCCCCCCOC(C)=O SUCYDSJQVVGOIW-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- IBXNCJKFFQIKKY-UHFFFAOYSA-N 1-pentyne Chemical compound CCCC#C IBXNCJKFFQIKKY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HXQSEFSDNBULLM-UHFFFAOYSA-M C(#CCCC)[Mg]Cl Chemical compound C(#CCCC)[Mg]Cl HXQSEFSDNBULLM-UHFFFAOYSA-M 0.000 description 1
- 241000659076 Grapholitha Species 0.000 description 1
- MFESCIUQSIBMSM-UHFFFAOYSA-N I-BCP Chemical compound ClCCCBr MFESCIUQSIBMSM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- MAAMIILYYYQTQW-OUKQBFOZSA-N [(e)-dodec-1-enyl] acetate Chemical compound CCCCCCCCCC\C=C\OC(C)=O MAAMIILYYYQTQW-OUKQBFOZSA-N 0.000 description 1
- TWWYPQIHQGTHLC-UHFFFAOYSA-J [Li].Cl[Cu](Cl)(Cl)Cl Chemical compound [Li].Cl[Cu](Cl)(Cl)Cl TWWYPQIHQGTHLC-UHFFFAOYSA-J 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- KSOUCCXMYMQGDF-UHFFFAOYSA-L dichlorocopper;lithium Chemical compound [Li].Cl[Cu]Cl KSOUCCXMYMQGDF-UHFFFAOYSA-L 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011981 lindlar catalyst Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003016 pheromone Substances 0.000 description 1
- 238000004262 preparative liquid chromatography Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はナシヒメシンクイガ(Oriental fr
uitmoth、 Gra holitha mole
sta )の性フエロモン成分であるシス−8−ドデセ
ニルアセテートの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is directed to Oriental fr.
Uitmoth, Gra holitha mole
The present invention relates to a method for producing cis-8-dodecenyl acetate, which is a sex pheromone component of sta).
(従来技術と発明が解決しようとする課題)近年、殺虫
剤等の農薬はそれを扱う者に対する毒性が大きく一つの
社会問題に発展している。この問題に対処するため、生
物学的害虫防除が研究されており、この方法の1つとし
て害虫のメスが放出する性フエロモンを化学的に合威し
、これを利用する交信撹乱防除法が提案されている。こ
の防除法はりん翅目害虫において研究が進んでおり最近
はフェロモン農薬として登録されるものも出始めていて
実用段階に入ってきている。(Prior art and problems to be solved by the invention) In recent years, agricultural chemicals such as insecticides have developed into a social problem due to their toxicity to those who handle them. To deal with this problem, biological pest control is being researched, and one proposed method is to chemically combine sex pheromones released by female pests and use this to control communication disruption. has been done. Research is progressing on this control method for Phosphoroptera pests, and recently some have begun to be registered as pheromone pesticides, and are entering the practical stage.
ナシヒメシンクイガ(Grapholitha mol
esta)の性フエロモン成分の一つであるシス−8−
ドデセニルアセテートは分子内に二重結合を1つ有する
直鎖状不飽和脂肪族化合物である。この合成方法は■ウ
ィッチヒ(Vitlig)反応を利用するもの(丁et
ra−hedron、 33,1845(1977)、
■液体アンモニア中、ナトリウムアルキルアセチリドま
たはりチウムアルキルアセチリドとアルキルイオダイド
とをカップリングさせ、炭素数を伸長する方法(Hol
anら、LISP 3,906,035)があるが、■
の場合1反応により生成するオレフィン化合物の幾fp
T純度が一般に低く、高いシス体純度を得るには細心の
注意を払った工夫を行なう必要があるし、■の場合には
、溶媒として液体アンモニアを使用する必要があり、低
温反応(−40℃〜−20℃)で耐圧装置が必要となり
、上記2方法共に工業的、経済的には必ずしも満足しう
るものではなかった。Grapholitha mol
cis-8-, one of the sex pheromone components of
Dodecenyl acetate is a linear unsaturated aliphatic compound having one double bond in the molecule. This synthesis method uses ■Vitlig reaction (Ding et al.
ra-hedron, 33, 1845 (1977),
■ A method of increasing the number of carbon atoms by coupling sodium alkyl acetylide or lithium alkyl acetylide with alkyl iodide in liquid ammonia (Hol
an et al., LISP 3,906,035), but ■
In the case of 1 reaction, how many fp of olefin compounds are produced?
The T purity is generally low, and in order to obtain a high cis isomer purity, it is necessary to take careful measures.In the case of (°C to -20°C), and both of the above two methods were not necessarily satisfactory from an industrial and economical point of view.
従って工業的に簡便かつ経済的に幾何純度の高いシス−
8−ドデセニルアセテートの製造方法が求められていた
。Therefore, it is industrially simple and economically possible to obtain a system with high geometric purity.
There was a need for a method for producing 8-dodecenyl acetate.
(課題を解決するための手段)
本発明者らは、この問題を解決すべく鋭意検討を行なっ
た結果CH,(CH,)CH=CH(CH,)、−C1
で示される シス−3−へブテニルクロリドのグリニヤ
ール試薬と 1−ブロモ−5−クロロペンタンとを L
iCuCl2および/またはLi、CuC14の存在下
で反応させて新規な中間体であるシス−8−ドデセニル
クロリドとし、ついで、これをアセチル化することによ
り効率良くシス−8−ドデセニルアセテートが得られる
ことを見出し本発明を完成した。(Means for Solving the Problem) As a result of intensive studies to solve this problem, the inventors found that CH, (CH,)CH=CH(CH,), -C1
Grignard reagent of cis-3-hebutenyl chloride and 1-bromo-5-chloropentane represented by L
By reacting in the presence of iCuCl2 and/or Li, CuC14 to form a new intermediate, cis-8-dodecenyl chloride, and then acetylating this, cis-8-dodecenyl is efficiently produced. They discovered that acetate could be obtained and completed the present invention.
以下、本発明の詳細な説明すると、この反応の出発物質
は入手容易なシス−3−ヘプテニルクロリドで、これは
以下の方法で容易に合成される。Hereinafter, the present invention will be described in detail. The starting material for this reaction is easily available cis-3-heptenyl chloride, which is easily synthesized by the following method.
c++、(cH2)2cミCH+CH,MgCICH,
(CH,)2CミCMgC1≦ミ5弓Q亡5dtCH,
(CH,)2CH=CH□(cH2)20Hjm(吐涜
九CH□(CH,)、CH=CH(CH2)2Cl常法
通りメチルマグネシウムクロリドのテトラヒドロフラン
溶液を調製し、これに1−ペンチンを撹拌下に滴下反応
させ、得られる1−ペンチニルマグネシウムクロリドに
エチレンオキシドを反応さ・せ、次いで加水分解反応さ
せることによりシス−3−ヘプチン−1−オールを生成
させる。このものをリンドラ−触媒を用いて水素添加し
たのち、塩化チオニルなどの塩素化剤で塩素化すること
により高収率でシス−3−ヘプテニルクロリドが得られ
る。このシス−3−ヘプテニルクロリドは無水テトラヒ
ドロフラン中、常法にて金属マグネシウムと40〜66
℃で反応させることにより、シス−3−へブテニルマグ
ネシウムクロリドのテトラヒドロフラン溶液へと導くこ
とができる。c++, (cH2)2cmiCH+CH, MgCICH,
(CH,)2CmiCMgC1≦mi5bowQde5dtCH,
(CH,)2CH=CH□(cH2)20Hjm(9 CH□(CH,), CH=CH(CH2)2Cl A tetrahydrofuran solution of methylmagnesium chloride was prepared in the usual manner, and 1-pentyne was stirred into it. The resulting 1-pentynylmagnesium chloride is reacted with ethylene oxide, and then hydrolyzed to produce cis-3-heptyn-1-ol.This product is reacted using a Lindlar catalyst. Cis-3-heptenyl chloride can be obtained in high yield by hydrogenation and subsequent chlorination with a chlorinating agent such as thionyl chloride.This cis-3-heptenyl chloride can be prepared by a conventional method in anhydrous tetrahydrofuran. metal magnesium and 40-66
By reacting at °C, it is possible to lead to a solution of cis-3-hebutenylmagnesium chloride in tetrahydrofuran.
一方、上記グリニヤール試薬と反応させる1−ブロモ−
5−クロロペンタンであるが、これは対応するα、ω−
アルカンジオール、すなわち1,5−ベンタンジオール
をヘプタンまたはトルエン溶媒存在下、濃塩酸化と混合
し還流下撹拌したのち、有機層を分液、減圧蒸留するこ
とにより5−クロロ−1−ペンタノールが得られる。次
に、この5−クロロ−1−ペンタノールと赤りんとを混
合し、この反応系に反応温度20℃以下で臭素を滴下し
たのち60℃で撹拌し反応液を減圧蒸留することにより
高収率で1−ブロモ−5−クロロペンタンが得られる。On the other hand, 1-bromo-
5-chloropentane, which has the corresponding α, ω-
Alkanediol, i.e. 1,5-bentanediol, is mixed with concentrated salt oxidation in the presence of heptane or toluene solvent and stirred under reflux, then the organic layer is separated and distilled under reduced pressure to produce 5-chloro-1-pentanol. can get. Next, this 5-chloro-1-pentanol and red phosphorus are mixed, bromine is added dropwise to the reaction system at a reaction temperature of 20°C or less, the mixture is stirred at 60°C, and the reaction solution is distilled under reduced pressure to achieve a high yield. 1-bromo-5-chloropentane is obtained.
この1−ブロモ−5−クロロペンタンとシス−3−へブ
テニルマグネシウムクロリドとを反応させることにより
新規な中間体シス−8−ドデセニルクロリドを生成させ
るのであるが、この反応にあたっては 1−ブロモ−5
−クロロペンタンのテトラヒドロフラン溶液中、触媒と
してL i Cu Cl□(リチウム塩化銅)またはL
i2CuCl4にリチウム四塩化銅)の存在下、前記グ
リニヤール試薬を反応温度O〜40℃にて滴下反応させ
ることにより目的のシス−8−ドデセニルクロリドが高
収率で得られる。A new intermediate, cis-8-dodecenyl chloride, is produced by reacting this 1-bromo-5-chloropentane with cis-3-hebutenylmagnesium chloride. -Bromo-5
- In a solution of chloropentane in tetrahydrofuran, L i Cu Cl□ (lithium copper chloride) or L
The desired cis-8-dodecenyl chloride can be obtained in high yield by dropping the Grignard reagent into i2CuCl4 in the presence of lithium copper tetrachloride at a reaction temperature of 0 to 40°C.
CH,(C:H,)、CH=CH(CH,)、MgC1
+Br(CH,)2Cl−−一一一→CH3(CH−)
−CH=CH(CHz)tCl +hAgBrC1上記
反応において反応モル比はシス−3−へブテニルマグネ
シウムクロリド1モルに対し 1−ブロモ−5−クロロ
ペンタンを0.9〜1.1モルとすることがよく、触媒
のLiCuCl2またはLi2CuCl4は0.003
〜0.02モル使用するのがよい。このようなりロスカ
ップリング反応させることにより得られた反応液を塩化
アンモン塩酸水溶液で加水分解し、その有機層を取り出
し、これを濃縮したのち、蒸留することにより目的とす
るシス−8−ドデセニルクロリドが高収率で得られる。CH, (C:H,), CH=CH(CH,), MgC1
+Br(CH,)2Cl--111→CH3(CH-)
-CH=CH(CHz)tCl +hAgBrC1 In the above reaction, the reaction molar ratio may be 0.9 to 1.1 mol of 1-bromo-5-chloropentane per 1 mol of cis-3-hebutenylmagnesium chloride. Often, the catalyst LiCuCl2 or Li2CuCl4 is 0.003
It is preferable to use 0.02 mol. The reaction solution obtained by such a loss coupling reaction is hydrolyzed with an aqueous ammonium chloride hydrochloric acid solution, the organic layer is taken out, concentrated, and distilled to obtain the target cis-8-dode. Cenyl chloride is obtained in high yield.
このクロスカップリング反応はグリニヤール試薬と炭素
−臭素結合をもった、または炭素−ヨウ素結合をもった
アルカン化合物との間で起こるが、グリニヤール試薬と
炭素−塩素結合をもったアルカン化合物との間では起こ
らない。本発明の場合1−クロロ−5−ブロモヘプタン
を使用するためα、ω−ジブロモアルカン、すなわち1
.5−ジブロムペンタンとグリニヤール試薬とのカップ
リング反応に比べて選択性、収率がよい。This cross-coupling reaction occurs between a Grignard reagent and an alkane compound having a carbon-bromine bond or a carbon-iodine bond, but between a Grignard reagent and an alkane compound having a carbon-chlorine bond. It doesn't happen. In the present invention, since 1-chloro-5-bromoheptane is used, α,ω-dibromoalkane, i.e. 1
.. It has better selectivity and yield than the coupling reaction between 5-dibromopentane and Grignard reagent.
3CH,(CH2)、CH=C:H(CH2)2MgC
1+2Br(CH2)、Br最後のアセチル化工程であ
るが、上記反応で得られたシス−8−ドデセニルクロリ
ドは、氷酢酸中、酢酸カリウムと反応すればアセテート
体へ導くことができる。3CH, (CH2), CH=C:H(CH2)2MgC
1+2Br (CH2), the final acetylation step of Br, cis-8-dodecenyl chloride obtained in the above reaction can be led to an acetate form by reacting with potassium acetate in glacial acetic acid.
cOK
CH,(CH,)、CH=CH(CH2)sCIAoo
HOH3(CH,)2CH=CH(CH,)、○C0C
H。cOK CH, (CH,), CH=CH(CH2)sCIAoo
HOH3(CH,)2CH=CH(CH,),○C0C
H.
反応はシス−8−ドデセニルクロリド1モルに対し酢酸
カリウム200〜400 g 、氷酢酸150〜400
gを用いて、撹拌しながら150〜180℃で4〜IO
時間行なえばよい。反応後は水和し、得られた有If&
層は減圧蒸留、シリカゲルカラムクロマトグラフィ、高
速分取液体クロマトグラフィなどの通常の単離操作で容
易にシス−8−ドデセニルアセテートを得ることかでき
る。The reaction was performed using 200-400 g of potassium acetate and 150-400 g of glacial acetic acid per mole of cis-8-dodecenyl chloride.
4 to IO at 150 to 180 °C with stirring using g
All you have to do is take your time. After the reaction, it is hydrated and the obtained compound If&
Cis-8-dodecenyl acetate can be easily obtained from the layer by conventional isolation operations such as vacuum distillation, silica gel column chromatography, and high-performance preparative liquid chromatography.
(実施例) 以下にその実施例を示す。(Example) Examples are shown below.
実施例=1シスー8−ドデセニルアセテートの合成内容
積IQの反応器に金属マグネシウム24g(1モル)、
無水テトラヒドロフラン360gおよびヨウ素1片を仕
込み、この混合物中に内温40℃にてシス−3−ヘプテ
ニルクロリド132.5g (1モル)を2時間で滴下
した。滴下終了後、さらに1時間60℃にて撹拌し反応
を完結させたのち20℃まで冷却し、この反応液(グリ
ニヤール試薬)を滴下ロートに仕込んだ。一方、2Q内
容積の反応器に 1−ブロモ−5−クロロペンタン18
5.5 g (1モル)と、Li2CuCl4のテトラ
ヒドロフラン溶液(LiC1430■とCuC1□67
6■をテトラヒドロフラン200 gに溶解したもの)
を仕込んでおき、これに上記グリニヤール試薬を内温i
0〜15℃にて滴下した。滴下終了後40℃にて1時間
撹拌し反応を完結させた。Example = 1 Synthesis of cis-8-dodecenyl acetate 24 g (1 mol) of metallic magnesium was placed in a reactor with an internal volume of IQ.
360 g of anhydrous tetrahydrofuran and 1 piece of iodine were charged, and 132.5 g (1 mol) of cis-3-heptenyl chloride was added dropwise to this mixture over 2 hours at an internal temperature of 40°C. After completion of the dropwise addition, the mixture was further stirred at 60° C. for 1 hour to complete the reaction, and then cooled to 20° C., and the reaction solution (Grignard reagent) was charged into the dropping funnel. On the other hand, in a reactor with an internal volume of 2Q, 1-bromo-5-chloropentane 18
5.5 g (1 mol) and a solution of Li2CuCl4 in tetrahydrofuran (LiC1430■ and CuC1□67
6■ dissolved in 200 g of tetrahydrofuran)
and add the Grignard reagent to it at internal temperature.
It was added dropwise at 0 to 15°C. After the dropwise addition was completed, the mixture was stirred at 40° C. for 1 hour to complete the reaction.
反応液を塩酸−塩化アンモニウム水溶液中に注ぎ、加水
分解したのち有機層を分液し、これを濃縮減圧蒸留した
ところ、シス−8−ドデセニルクロリドが168 g
(収率83%)得られた。このようにして得られたシス
−8−ドデセニルクロリド168 g 、氷酢酸250
gおよび酢酸カリウム295gを内容積IQの反応器
に仕込み撹拌しながら還流温度(164℃)で9時間反
応させた。反応終了後100℃以下に冷却し、水300
m Qを加えたのち有機層を分液して、これを減圧蒸留
したところ、シス−8−ドデセニルアセテートが170
g (収率90%)得られた。The reaction solution was poured into a hydrochloric acid-ammonium chloride aqueous solution, and after hydrolysis, the organic layer was separated, and this was concentrated and distilled under reduced pressure. As a result, 168 g of cis-8-dodecenyl chloride was obtained.
(yield: 83%). 168 g of cis-8-dodecenyl chloride thus obtained, 250 g of glacial acetic acid
g and 295 g of potassium acetate were charged into a reactor having an internal volume of IQ and reacted for 9 hours at reflux temperature (164° C.) with stirring. After the reaction is completed, cool to 100℃ or less and add 300℃ of water.
After adding mQ, the organic layer was separated and distilled under reduced pressure, resulting in 170% of cis-8-dodecenyl acetate.
g (yield 90%) was obtained.
実施例2:シスー8−ドデセニルアセテートの合成L
i、 Cu C14のテトラヒドロフラン溶液の代わり
にLiCuCl□のテトラヒドロフラン溶液(LL−C
1430■とCuC1996■をテトラヒドロフラン2
00gに溶解したもの)を使用したほかは実施例1と全
く同様の操作を行なったところシス−8−ドデセニルク
ロリドがtssg(収率81.5%)、つづくアセチル
化反応でシス−8−ドデセニルアセテートが166g(
収率90%)得られた。Example 2: Synthesis of cis-8-dodecenyl acetate L
i, LiCuCl□ in tetrahydrofuran solution (LL-C
1430■ and CuC1996■ in tetrahydrofuran 2
The same procedure as in Example 1 was carried out except that cis-8-dodecenyl chloride was used (dissolved in 81.5% of cis-8-dodecenyl chloride). 166g of 8-dodecenyl acetate (
90% yield) was obtained.
比較例
実施例1におけるシス−3−へブテニルクロリド132
.5 g (1モル)と1−ブロモ−5−クロロペンタ
ン185.5g(1モル)に代えて、それぞれシス−3
−へブテン−1−クロリド132.5 g (1モル)
と1−ブロモ−3−クロロ−プロパン157.5 g
(↓モル〉を使用したほかは実施例1と同様にして反応
を行ったところ、シス−5−デセン−l−クロリドが1
45g(収率83%)で得られた。しかし、この中には
副生物として■。Comparative Example Cis-3-hebutenyl chloride 132 in Example 1
.. 5 g (1 mol) and 185.5 g (1 mol) of 1-bromo-5-chloropentane, respectively, with cis-3
-hebutene-1-chloride 132.5 g (1 mol)
and 157.5 g of 1-bromo-3-chloro-propane
(↓mol) The reaction was carried out in the same manner as in Example 1, except that cis-5-decene-l-chloride was
Obtained in an amount of 45 g (83% yield). However, some of this is ■ as a by-product.
6−ゾカジエンが2%含まれているため、この分離のた
めに精留塔で再蒸留したところ、精製されたシス−5−
デセン−1−クロリドが132g(収率91%)で得ら
れた。Since it contains 2% 6-zocadiene, it was redistilled in a rectification column for this separation, resulting in purified cis-5-
132 g (yield 91%) of decene-1-chloride was obtained.
ついで、精製したシス−5−デセン−1−クロリドを実
施例1と同様にしてテトラヒドロフラン中でグリニヤー
ル試薬を作り、この中にエチレンオキサイド75gを2
0〜30℃で撹拌しながら滴下反応した後、塩化アンモ
ニウム240g、濃塩酸L6Qmgを加えた水溶液80
0m1l中に注いで加水分解し、有機層を減圧蒸留し、
シス−8−ドブセノール80.7g (収率55%)を
得た。これをピリジン200 ailに溶解し、無水酢
a50gを加え60℃で2時間撹拌した後、水500d
に注ぎ有機層を減圧蒸留したところ、シス−8−ドデセ
ニルアセテートを94g(収率95%)得た。Next, a Grignard reagent was prepared from the purified cis-5-decene-1-chloride in tetrahydrofuran in the same manner as in Example 1, and 75 g of ethylene oxide was added to the Grignard reagent in the same manner as in Example 1.
After a dropwise reaction with stirring at 0 to 30°C, 80 g of an aqueous solution containing 240 g of ammonium chloride and L6Q mg of concentrated hydrochloric acid was added.
Pour into 0ml for hydrolysis, distill the organic layer under reduced pressure,
80.7 g (yield 55%) of cis-8-dobcenol was obtained. Dissolve this in 200 ails of pyridine, add 50g of anhydrous vinegar A, stir at 60°C for 2 hours, and then add 500d of water.
When the organic layer was distilled under reduced pressure, 94 g (yield: 95%) of cis-8-dodecenyl acetate was obtained.
しかし、このものはシス体の純度95%で、トランス体
5%を含んでいた。However, this product had a purity of 95% in cis form and contained 5% in trans form.
結局、本比較例ではシス−3−へブテン−1−クロリド
よりシス−8−ドデセニルアセテートまで3工程、収率
39.5%であり、シス体の純度も95%であったが、
実施例上はシス−3−へブテニルクロリドよりシス−8
−ドデセニルアセテートまで2工程、収率75%であり
、シス体の純度も約100%と高いものであった。In the end, in this comparative example, it took 3 steps to convert cis-3-hebutene-1-chloride to cis-8-dodecenyl acetate, with a yield of 39.5%, and the purity of the cis-isomer was 95%. ,
In the example, cis-8 is preferable to cis-3-hebutenyl chloride.
-Dodecenyl acetate was obtained in two steps with a yield of 75%, and the purity of the cis isomer was also as high as about 100%.
Claims (1)
で示されるシス−3−ヘプテニルクロリドのグリニャー
ル試薬と1−ブロモ−5−クロロペンタンとをLiCu
Cl_2および/またはLiCuCl_4の存在下で反
応させてシス−8−ドデセニルクロリドとし、ついでこ
れをアセチル化することを特徴とするシス−8−ドデセ
ニルアセテートの製造方法。CH_3(CH_2)CH=CH(CH_2)_2Cl
A Grignard reagent of cis-3-heptenyl chloride represented by
A method for producing cis-8-dodecenyl acetate, which comprises reacting in the presence of Cl_2 and/or LiCuCl_4 to form cis-8-dodecenyl chloride, which is then acetylated.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2254606A JPH0633243B2 (en) | 1982-04-12 | 1990-09-25 | Method for producing cis-8-dodecenyl acetate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57060692A JPS58177924A (en) | 1982-04-12 | 1982-04-12 | Preparation of cis-alkenyl chloride |
JP2254606A JPH0633243B2 (en) | 1982-04-12 | 1990-09-25 | Method for producing cis-8-dodecenyl acetate |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57060692A Division JPS58177924A (en) | 1982-04-12 | 1982-04-12 | Preparation of cis-alkenyl chloride |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03173849A true JPH03173849A (en) | 1991-07-29 |
JPH0633243B2 JPH0633243B2 (en) | 1994-05-02 |
Family
ID=26401752
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2254606A Expired - Lifetime JPH0633243B2 (en) | 1982-04-12 | 1990-09-25 | Method for producing cis-8-dodecenyl acetate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0633243B2 (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51125204A (en) * | 1975-01-22 | 1976-11-01 | Mitsubishi Petrochem Co Ltd | Process for preparation of olefin derivatives containing oxygen atom |
JPS56100727A (en) * | 1980-01-14 | 1981-08-12 | Shin Etsu Chem Co Ltd | Cis-6-undecene-1-chloride and its preparation |
-
1990
- 1990-09-25 JP JP2254606A patent/JPH0633243B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51125204A (en) * | 1975-01-22 | 1976-11-01 | Mitsubishi Petrochem Co Ltd | Process for preparation of olefin derivatives containing oxygen atom |
JPS56100727A (en) * | 1980-01-14 | 1981-08-12 | Shin Etsu Chem Co Ltd | Cis-6-undecene-1-chloride and its preparation |
Also Published As
Publication number | Publication date |
---|---|
JPH0633243B2 (en) | 1994-05-02 |
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